Higher aldehyde derivatives of reaction products of aldehydes and amines and process of making same



Patented Mar. 8, 1921.

UNITED STATES CLAYTON 'OLIN NORTH, 01 'IALLMADGE TOWNSHIP, SUMMITCOUNTY, OHIO.

HIGHER ALDEHYDE DERIVATIVES 0F REACTION PRODUCTS 01 ALDEEYDEQ AMINES ANDPROCESS OF MAKING SAME.

I No Drawing. Original application flled I Iarch 24, 1928, Serial No.627,825. Divided and this application filed March 5, 1928. Serial No.92,616.

This application is a division of my application Serial No.627,325ffi1ed March 24, 1923.

My invention relates to a process of reacting aliphatic aldehydes higherthan formaldehyde with condensation products of aromatic primary aminesand aliphatic aldehydes, and particularly reacting acetaldehyde with thecondensation product of 3 moles of acetaldehyde and 2 moles of aniline,

- The invention also comprises the new materials obtained. v

A method of making a compound in which 3 moles of acetaldehydearecombined with 2 moles of aniline is set forth in my copendingapplication Serial No. 627 .326, filed on March 24. 1923. The compoundso produced is believed to be in the nature of, or closely related inchemical constitution'to. derivatives of tetrahydro-quinoline, whichpossesses what I'choose to call a reactive methyl group, having theproperty of condensing with one or more molecules of an aldehyde toproduce further products.

According to thepreferable mode of pr0- cedure. acetaldehyde is reactedwith aniline to produce a compound in which 3 moles of acetaldehyde arecombined with 2 moles of aniline, as claimed inmv aforementionedappli'cation Serial No. 627,326. and the material so obtained isdehydrated by evaporation at temperatures no higher than 105 0., untilthe moisture content is substantially reduced. 'Advantageously thedehydration maybe continued until the moisture content is. approximately2%; I have found that this dehydrated compound will react with furtheraldehyde and in particular with aliphatic aldehydes higher thanformaldehyde, 1

as acetaldehyde and still higher aldehydes. Dehydration of this compoundto a substantial' extent, at least, is necessary for obtaining optimumyields, the presence of water in substantial proportions apparentlybeing unfavorable to the reaction of aliphatic aldehydes aboveformaldehyde upon this .compound.

One example of the ways in which a process within my invention can becarried out is the following:

132 parts of the dehydrated condensation p'roductof acetaldehyde andaniline above described are refluxed with 79.5 parts of aoetaldehyde fora period of about 14 or 15 hours at a temperature above the boiling-po1nt of the aldehyde, but below the boiling point of water. Therefluxing period can be reduced by use of efiicient heating means. Atthe end of the reaction period I preferably discontinue the refluxing,and heat to a temperature of not over 105 (1., to evaporate the waterand remove the excess aldehyde. In order to avoid frothing and foam ingI may pass a current of air through the mass while the water is beingevaporated. When the water has been practically all removed it is oftenadvantageous to heat at a somewhat higher temperature for a perio ofabout hour on less, but in no case is it advisable to heat above about115 C. The resinous product so obtained contains approximately 2% ofmoisture, is hard and vitreous, and can be readily ground and sifted. Asimilar change takes place when acetale dehyde is reacted substantiallyas disclosed above with the primary aldehyde derivative of anhydroformaldehyde aniline, or with i the primary aldehyde derivative of thecondensation product formed 'bythe interaction of aliphatic aldehydes,such as formaldehyde on acetaldehyde on primary amines such as aniline.o-toluidine, m-toluidine, p-toluidine, the xylidines, aminocymene', etc.The quantity of aldehyde taken td'combine with the aldehyde-aminecondensation product is preferably in excess of that actually requiredto complete the change.

Although -'n the example given I have specified the use of acetaldehydeon the dehydrated combination product of 3 moles of acetaldehyde and 2moles of aniline, it is to be understood that my invention is notlimited solely to this, but that other similarly constituted materialsand compounds may be used. Broadly my invention comprises themanufacture of a compound by condensation reaction of an aliphaticaldehyde aboveformaldehyde with the condensation product ofaliphatic-aldehydes and aromatic primary amines.

I claim: 1. A hard resinous compound formed by the action ofacetaldehyde on the reaction product of 3 moles of acetaldehyde with 2moles of aniline.

2. The process of making a hard resinous compound, which comprisesreacting acetaldehyde with the reaction product of 3 moles ofacetaldehyde with 2 moles of aniline.

3. A hard resinous compound formed by the action of acetaldehyde on thedehydrated reaction product of 3 moles of acetaldehyde with 2 moles ofaniline.

4. The process of making a hard resinous compound, which comprisesreacting acetaldehyde with the dehydrated reaction product of. 3 molesof acetaldehyde with 2 moles of aniline.

5. A hard resinous compound formed by the action of acetaldehyde on thedehydrated reaction product of acetaldehyde and aniline.

6. The process of making a hard resinous compound, which comprisesreacting acetaldehyde on the dehydrated reaction product of acetaldehydeand aniline.

7. A. hard resinous compound formed by the action of an aliphaticaldehyde higher than formaldehyde on the dehydrated reaction product of3 moles of acetaldehyde with 2 moles of aniline.

12. 'The process of making a resinous-ma-v terial. which comprisesreacting acetaldehyde and aniline in the proportion of substan tially 3moles of acetaldehvde to 2 moles of aniline, evacuating water from theproduct so obtained, introducingacetaldehyde into said product in theproportion of approximately 79.5 parts of acetaldehyde to 132 parts ofsaid product, refluxing the mixture at a temperature above the boilingpoint of acetaldehyde and below the boiling point of water for severalhours, evacuating water,

then :turther heating at a temperature not to exceed 115 (3., and thencooling and grinding.

.13. Ahard resinous compound formed by reacting approximately 79.5 partsof acetaldehyde with approximately 132 parts of the dehydrated reactionproduct of 3 moles of acetaldehyde and 2 moles of aniline.

14. The process of making a hard resinous compound. which comprisesreacting approximately? 9.5 parts of acetaldehyde with approximately 132parts of the dehydrated reaction. product of 3 moles of acetaldehyde and2 moles of aniline.

In testimony whereof, I have signed my name hereto.

CLAYTON OLIN NORTH.

